Theic-hydantoin-ester resins for wire coatings

ABSTRACT

Resin composition useful as a wire coating comprising the reaction product of a reactive hydantoin based compound, a polycarboxylic acid, and tris (2-hydroxyethyl) isocyanurate. The resin provides a low cost, cured enamel for electrical conductors. Preferably, the resin composition includes another polyhydric alcohol such as ethylene glycol to impart flexibility.

United States Patent 1191 1111 3,835,121 Preston Sept. 10, 1974 THEIC-HYDANTOIN-ESTER RESINS FOR [56] References Cited WIRE COATINGS UNITED STATES PATENTS Inventor: Jerome Preston, Angola, 3,397,253 8/1968 Merten et a1 260/77.5 NC 3,681,282 8/1972 Preston 260/D1G. 34 [73] Asslgnee' Essex lniegmmnal Fm 3,737,432 6/1973 George etal 260/77.5 NC Wayne 3,779,991 12/1973 Preston 260/010. 34 [22] Filed: Oct. 3, 1973 Primary Examiner-Melvyn I. Marquis [21] Appl' 402977 Attorney, Agent, or Firm-Molinare, Allegretti, Newitt Related US. Application Data & Witcoff [63] Continuation-impart of Ser. No. 275,922, July 18, Y

1972, Pat. No. 3,779,991, which is a continuation-in-part of Ser. No. 58,173, July 24, [57] ABSTRACT 1970, ,282. Resin composition useful as a wire coating comprising the reaction product of a reactive hydantoin based 1 117/132 260/ 18 T, compound, a polycarboxylic acid, and tris (2- R, 60/336 UB, 2 0/ hydroxyethyl) isocyanurate. The resin provides a low NH, 260/77.5 R cost, cured enamel for electrical conductors. Prefera- [51] Int. Cl C08g 22/08 bly, the resin composition includes another polyhydric [58] Field of Search 260/DIG. 34, 77.5 B, 77.5 NC,

260/75 NH; 117/132 R alcohol such as ethylene glycol to impart flexibility.

10 Claims, No Drawings TI-IEIC-I-IYDANTOIN-ESTER RESINS FOR WIRE COATINGS CROSS REFERENCE TO RELATED APPLICATIONS BACKGROUND OF THE INVENTION This invention relates to novel polyester materials containing hydantoin radicals and isocyanurate radicals in the polymeric backbone.

There has been a continuing demand for an improved magnet wire enamel coating which possesses good electrical insulating properties, resistance to heat and solvent attacks, and other desirable properties. US. Pat. Nos. 3,211,585 and 3,342,780, disclose examples of such a polyester enamel for magnet conductors when these properties are obtained by utilizing the reaction product of a polycarboxylic acid and tris (2- hydroxyethyl) isocyanurate (THEIC).

These THEIC based resins are used for high temperature applications and have a high cost which is often prohibitively expensive. Thus, less expensive substitutes and partial substitutes for THEIC are desirable. For example, aliphatic polyhydric alcohols such as ethylene glycol or glycerine are often used as a partial substitute for THEIC for purposes of economy. The resultant resin has lesser quality, but is commercially acceptable because it has a lower cost.

Accordingly, it is an object of the present invention to provide a novel enamel coating for magnet wires less expensive than the THEIC based resins but having substantially equivalent properties in comparison to THEIC resins.

It is another object of this invention to provide an economic substitute for THEIC that provides a superior product when compared to the aliphatic polyhydric alcohol substituted THEIC polyesters.

It is a specific object of this invention to substitute at least a portion of the ethylene glycol in a THEIC based resin with a reactive hydantoin compound to improve resin properties.

Further objects of the invention will become apparent to those skilled in the art from a reading of the fol- I lowing description.

SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a new magnet wire coating which comprises a polymer containing both hydantoin rings and isocyanurate rings in the backbone.

As used herein, isocyanurate ring or radical as derived from THEIC refers to the radical as it appears in the polymer backbone.

In particular, the preferred novel polymers of the present invention having hydantoin and isocyanurate radicals in the resin backbone are the reaction product of a monomeric or polymeric compound containing a .hydantoin radical and having reactive OH, H,

-COOH, alkoxy, and NH groups and equivalents thereof; an aromatic carboxylic acid having at least two carboxy groups or an anhydride, ester, chloride of said acid and THEIC. In a more limited preferred embodiment up to 50 equivalent percent of the THEIC is rev placed by another polyhydricalcohol such as ethylene glycol.

Thus, the novel polymers of the invention may be 3 prepared by reacting THEIC, the carboxylic acid, and

V the reactive-hydantoin radical containing compound.

These reactions are affected by means known to the art. Preferred are reaction temperatures of about 150C. to about 280C. and reaction times of about 4 j hours to 24 hours.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As indicated, the novel polymers of the present invention are obtained by reacting a reactive hydantoin radical containing compound, a carboxylic acid and THEIC.

To provide a hydantoin radical defined as in the polymer backbone wherein A is H, OH, ROH, COOH, RCOOH, -NH

' (OR);,OH wherein R is (CH and y is l-5, x is an integer in the range of 1 to 10, R -O-R where R and R are C -C alkyl groups, and B is H, OH, ROH, COOH, RCOOH, NH RNH or a C C alkyl group.

Typical reactive hydantoin monomers are diphenyl hydantoin, dimethyl hydantoin, diethyl hydantoin, mono methylol dimethyl hydantoin, (dimethyl hydantoin methyl) amine, methylene bis dimethyl hydantoin, dicarboxydiethyl 5,5 dimethyl hydantoin, diamino dipropyl 5, 5 dimethyl hydantoin and dihydroxydiethyl 5, 5' dimethyl hydantoin. These monomers can be obtained from Glyco Chemicals, Inc., Greenwich, Conn. A particularly preferred hydantoin l, 3- dihydroxyethyl, 5, 5 dimethyl hydantoin.

The reactive hydantoin compound can be prepared, in an alternative embodiment, by reacting HCN and a diisocyanate, reacting N-phenylglycine esters with 3 phenylisocyanate or by reacting a glycine with a polyisocyanate, a polyisothiocyante or a polyamine.

While the previously described monomers are preferred, it is also within the scope of this invention to utilize dimers and trimers of these monomers. Preferably, the hydantoin comprises about 5 percent to about 50 percent by weight of the composition and affects a partial substitution for THEIC without materially adversely affecting the properties of the resin. Preferably, the Tl-lElC comprises about 5 percent to about 50 percent by weight of the composition.

The last method indicated for making a reactive hydantoin containing component herein and the glycine derivatives which are suitable are disclosed in the Merten et al. US. Pat. No. 3,397,253. It may be stated generally such glycine derivatives are prepared by the reaction of an aromatic polyamine with a haloacetic acid. Representive examples of such glycine derivatives are: N,N-bis-carbethoxymethyl-4-4' diamino diphenyl methane; N,N-bis-carbethoxymethyl-4-4 diamino diphenyl ether.

Preferred glycine derivatives for this embodiment are compounds of the general formula:

wherein Ar represents an aromatic radical, Z repre sents hydrogen or COR R, represents hydrogen or alkyl, R represents the hydroxyl group or an amino group, an alkylamino-, dialkylamino-, alkoxy-, or aroxy group and x is an integer between 2 and 4. R represents a dialkylamino group, an alkoxy group or an aroxy group. The glycine derivatives used according to the invention should contain the radical [bl-2 0 O 13 at least twice in the molecule.

The aromatic radical Ar is preferably a radical derived from benzene, azobenzene, naphthalene, anthracene, diphenyl, triphenylmethane, a diphenylalkane, a diphenylalkene, diphenylether, diphenylthioether or a polyphenylether. These radicals may also be substituted once or several times, for example, by alkyl- (methyl-) halogen- (chloro-), nitro-, alkoxy- (methoxydialkylamino- (dimethylamino-). acyl- (acetyl-), carbalkoxy- (carbomethoxy or -ethoxy) and cyano groups. Benzene-, naphthalene-, diphenylmethaneand diphenylether derivatives which may be substituted once or twice by methyl groups and/or chlorine atoms are preferred.

The preparation of the glycine derivatives used as starting materials is known and may, for example, be carried out by direct reaction of aromatic polyamines with haloacetic acids or derivatives thereof or by condensation with hydrocyanic acid and aldehydes or ketones, followed by conversion of the nitrile group, into for example, carboxylic acid, ester or amide.

The reaction of aromatic polyamines with haloacetic acid or its derivatives is carried out in an organic solvent, e.g., in ethanol, methanol, acetone, benzene or in an aqueous medium with the use of acid binding agents such as tertiary amines (e.g. pyridine, triethylamine), excess starting amine, soda, potash, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, calcium oxide or calcium carbonate.

Suitable haloacetic acids or derivatives thereof are, for example, chloroacetic acid, chloroacetamide, N, N-dialkylchloroacetamide (alkyl being preferably methyl, ethyl, butyl), chloroacetic acid esters (e.g. methyl, ethyl, phenyl esters), a-chloropropionic acid esters and a-chloropropionic acid.

Another method consists in condensing aryl polyamines with cyanides (e. g. NaCN, KCN) and oxo compounds (e.g. formaldehyde, acetone, acetophenone) with addition of acids; the nitriles obtained can then be saponified in known manner to form carboxylic acids or converted directly into esters by means of alcoholic hydrochloric acid. Other processes consist in modifying glycine derivatives already prepared, e.g. by esterification of the free acids or aminolysis of the esters.

Suitable aromatic polyamines for use in the invention are compounds having at least two amino groups bound to aromatic nuclei although these must not be arranged in the 0- or peri-position. Furthermore, the amines may be substituted in any way desired. Examples of such aromatic polyamines are the following:

mand pphenylene diamine,

2,4-, 2,5- and 2,6- toluylene diamine, diisopropylbenzene diamines,

l, 3, 5 triaminobenzene,

2, 4, 6 triaminotoluene, 4,4-diaminoazobenzene,

2, 4, 6- triaminoethylbenzene,

l ,3,5-triisopropylbenzene-diamines, 2-chloro-1 ,4-phenylene diamine, 2,5-dichloro-1,4-phenylene diamine, 2,6-dichloro- 1 ,4-phenylene diamine, 2,6-diamino-and 4,6-diamino-5-methyl-1,3-diethyl -benzene, 3 1 2,4, 2,5, 2,7- and 2,8- diaminonaphthalene,

1 ,4-diaminoanthraquinone, l ,5-diaminoanthraquinone, 4,4'-and 2,4'-diamino diphenyl methane 4,4-and 2,4-diamino-diphenyl ether, 4,4-and 2,4'-diamino-diphenylthioether, 4,4-diamino-diphenyldisultide, 4,4-diamino-diphenyl, 4,4-diarnino-3,3 '-or -2,2'-dichlorophenyl, 4,4 '-diamino-3 ,3 '-dialkoxy-diphenyl, 4,4 '-diamino-3 ,3 '-dimethyl-diphenyl, 4,4'-diamino-diphenylmethane, 2,2-bis-p-aminophenyl-propane, l ,2-bis-p-aminophenyl-ethane, 4,4-diamino-stilbene, 4,4'-diamino-azobenzene, 4,4-diamino-diphenylsulfon, 4,4',4"-triamino-triphenylmethane, diamino-carbazole, 2,2 '-dichloro-4,4' '-diaminotriphenylether and 2,4-diamino-6-phenyl-( l ,3 ,5 )-triazine. High molecular weight compounds containing several aromatically bound amino groups e. g. aniline formaldehyde resins, may also be used.

Suitable polyisocyanates and polyisothiocyanates to be heated with the glycine derivatives are, for example, aliphatic, cycloaliphatic or aromatic compounds having at least two NCO- or NCS-groups in the molecule. The following are examples of such polyisocyanates: Polymethylene diisocyanates' of the formula ,OCN-(CH NCO wherein n is a number from 4 to 8, benzene diisocyanates which may be substituted with alkyl groups, for example mand pphenylene diisocyanates, toluylene- 2,4- and -2,6-diisocyanate, ethylbenzene-diisocyanates, diand tri-isopropyl benzene diisocyanates, chloro-pphenylene diisocyanates, diphenylmethane diisocyanates, naphthalene diisocyanates, ester isocyanates such as triisocyanato-arylphosphoric ester andthioester, glycol-di-p-isocyanatophenyl ester, 4, 4- diisocyanato-diphenylether, l ,Z-bis-p-isocyanatophenylethane and 4,4- diisocyanato-stilbene. Partially polymerized isocyanates having isocyanurate rings and free NCO groups may also be used.

The polyisocyanates may also be used in the form of their derivatives, e.g. the reaction products with phenols, alcohols, amines, ammonia, bisulphite, I-ICl etc. Individual examples of these are phenol, cresols, xylenol, ethanol, methanol, propanol, isopropanol, ammonia, methylamine, ethanolamine, dimethylamine, aniline and diphenylamine. Relatively high molecular weight addition products, e.g. of polyisocyanates with polyalcohols such as ethylene glycol propylene glycol, trimethylolalkanes or glycerol may also be used.

Instead of the polyisocyanates mentioned, the corresponding thio compounds may be used as well.

The process is generally carried out by heating the two starting components for some time in an organic solvent, the polymer produced remaining in solution. The polymer can be isolated by distilling off the solvent. The quantities of starting compounds may be so chosen that 0.5 to mols of isocyanate or isothiocyanate groups are available per mol of NH groups, and it is preferable to use 1 to 3 mols of isocyanate or isothiocyanate. Suitable solvents for the process are compounds which are inert to NCO groups, e.g. aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, esters and ketones.

Especially suitable are N-alkylpyrrolidones, dimethylsulphoxide, phenol, cresol and dimethylformamid. Where iso (thio) cyanate derivatives are used, other solvents, such as alcohols or phenols, may also be used. On the other hand, it is also possible to react the components together directly without the use of solvent.

The reaction times vary between 30 minutes and several days and may in special cases lie above or below these limits. The reaction temperatures are chosen to be between 0 and 500C., depending on the starting material.

It is preferred to work at to 350C, the best results being obtained in the region of 20 to 230C.

The condensation reactions'may be accelerated by the use of catalysts, e.g. metal alcoholates or tertiary amines.

In the polymerisation there takes place, in addition to the condensation of the two reactants, a ring closure reaction to form the hydantoin ring, as can be represented by the following reaction equation:

A hydantoin polymer used in this invention can contain the recurring unit liil wherein Ar corresponds to the definition already given, R represents hydrogen and alkyl having I to 6 carbon atoms and y is Ar and additionally alkyl having 4 to 10 carbon atoms (one or more of which may be replaced by oxygen and sulfur) and xylylene. This removing unit may be contained in the polymer about 20 to 5,000 times or more.

In another process for preparing the hydantoin polymers, derivatives of N-carboxy-glycine compounds are heated with polyamines to temperatures between and 500C. This heating may also be carried out in an organic solvent.

Preferred are N-carboxy-glycine derivatives of the general formula I COR R l co...l

COR R Ll t com] at least twice in the molecule.

The aromatic radicals Ar are preferably the radicals derived from benzene, azobenzene, naphthalene, anthracene, triphenylmethane, diphenylmethane or diphenylether. These radicals may carry one or several substituents for example alkyl-(methyl-), halogen- (chloro-), nitro-, alkoxy-(methoxy-), dialkylamino- (dimethylamino-), acyl-(acetyl-), carbalkoxy- (carbomethoxyor carboethoxy-) and cyano groups. It is advantageous to use the benzene, naphthalene, diphenylmethane or diphenylether derivatives which may be substituted, once or twice, by methyl and/or chloro functions. The glycine derivatives to be used as starting materials are prepared according to known methods. By the direct reaction of the corresponding aromatic polyamines with hydrocyanic acid and aldehydes or ketones and subsequent conversion of the nitrile group into the desired carboxyl function, for example carboxylic acid ester or amide or by condensation of the aromatic polyamines with haloacetic acid or derivatives thereof, there are obtained glycine derivatives having a free Nil-function which can subsequently be converted into the desired starting materials by means of chlorocarbonic acid alkylester or chlorocarbonic acid arylester. The reaction with the halogen acetic acid or derivatives thereof as well as the chlorocarbonic acid derivatives proceeds in the sense of a Schotten- Baumann reaction, for example in an organic solvent such as ethanol, methanol, acetone or benzene, or in an aqueous medium with the simultaneous use of an acid acceptor, for example a tertiary amine (pyridine, triethylamine), excess starting amine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium carbonate.

This procedure is essentially the same as already described.

The following condensation with chlorocarbonic acid alkylesters or chlorocarbonic acid arylesters, for example chlorocarbonic acid methyl-, -ethyl-, -propyl-, -phenylor tolylester, is carried out under substantially equal conditions. It is possible to successively combine several processing steps in one reaction step, for example, condensation reactions with chloroacetic acid derivatives and chlorocarbonic acid derivatives. Another method for the preparation of the glycine derivatives comprises condensing the corresponding carbamic acid esters having a free NH-group with a chloroacetic acid derivative, in general via the salt of the carbamic ester.

The thus obtained polyfunctional glycine derivatives containing at least twice the group li iilcom] are reacted at elevated temperature with a primary polyamine, i.e. a compound having at least two primary amino groups, yielding the polyhydantoins. The reaction can be represented for example by the following formula Suitable polyamines for the reaction with the above described glycine derivatives are for example aliphatic, cycloaliphatic and in particular aromatic compounds containing at least two primary amino groups in the molecule. As examples for these polyamines there are mentioned a, w -diaminoalkanes having two to 18 carbon atoms in the molecule, such as ethylene diamine, propylene diamine 1,2, and 1,3, l,4-diamino-butane, hexamethylene diamine, and octamethylene diamine, besides their alkyl substitution products and polymers, such as trimethyl-hexamethylene diamine, diethylene triamine, triethylene tetramine or dipropylene triamine, aminomethyl group-containing aromatics such as 1,3- or l,4-xylylene diamine as well as the aromatic polyamines mentioned with reference to the preparation of the glycine derivatives.

The compounds are generally formed by heating the two components, preferably in stoichiometric quantities to elevated temperature in order to effect the aminolysis represented by the above equation. This reaction is preferably carried out, at least towards the end of the reaction, in the presence of an aromatic solvent. Suitable solvents for this purpose are inert organic solvents such as aliphatics, aromatics, halogen hydrocarbons, in particular N-alkylpyrrolidones, dimethylformamide, dimethylacetamide, dimethylsulfoxide, phenol and cresols.

The condensation of the components is in general effected within the range between and 350C. preferably between and 200C, by preparing, first in the absence of a solvent, pre-condensation product the molecular weight of which is increased as the reaction progresses at elevated temperature. The condensation reaction can be activated by the use of an acidic, an alkaline or a metal catalyst (sodium carbonate, sodium hydroxide solution, endoethylene piperazine, triethylamine, phosphoric acid, p-toluene sulfonic acid, sodium phenolate, lead oxide or titanium tetrabutylate).

' The condensation degree of the resulting polymers containing several hydantoin groups in the molecule is determined by the choice of the quantitative ratio of the glycine derivative and the amino component as well as by the reaction conditions. Polymers of high molecular weight i.e. about above several thousand can immediately be taken up in a solvent at the end of the condensation or after the desired condensation degree has been achieved.

Particularly suitable are polycondensates containing hydantoin or thiohydantoin rings, which are linked through their nitrogen atoms by bivalent organic groups, such as alkylene groups containing 4 to 10 carbon atoms, phenylene groups, toluylene groups, diphenylene groups and diphenylether groups.

Although not essential, additional flexibility can be imparted to the final resin reaction product by the addition of a polyhydric alcohol in an amount up to 50 equivalent weight percent of the THEIC, and preferably in the amount of about 1 percent to about 10 percent by weight of the final product. Suitable polyhydric alcohols include both glycols and polyols.

The glycol employed can vary widely. In general, they are the glycols conventionally employed in preparing polyesters. Suitable examples include alkylene glycols of the formula H(OA),,OH where n is, for example, l-lO or higher and A is alkylene, such as ethylene, propylene, butylene, etc., for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, triethylene glycol, butylene glycol, tetramethylene glycol, neopentyl glycol, Z-methyl-l, 3-pentanediol, 1,5-pentanediol, hexamethylene glycol, xylylene glycol, etc. Preferably, one employs an alkanediol of the general formula HO(CH ),,OH where n=2-5 or isomers thereof wherein the alkane group is branched and/or the hydroxy groups are not terminal. The preferred glycol is ethylene glycol.

The polyols used in the preparation of the polyesters of this invention can be widely varied and are those containing at least three esterifiable hydroxyl groups. In general, these are the polyhydric alcohols conventionally employed in preparing polyesters. Illustrative examples of such alcohols are glycerol, polyglycerol, pentaerthritol, mannitol, trimethylopropane, trimethlolethane, l, 2, 6-hexanetriol, polypentaerythritol, polyallyl alcohol, polymethallyl alcohol, polyols formed by the condensation of bisphenols with epichlorohydrin, and the like.

Preferred polyhydric alcohols to be used in the preparation of these polyesters are the aliphatic alcohols possessing from 3 to 6 hydroxyl groups and containing from 3 to 14 carbon atoms, such as glycerol, pentaerythritol, mannitol, l, 4, 6-octanetriol, l, 3, 5- hexanetriol and l, 5, lO-dodecanetriol.

A variety of monocyclic aromatic polycarboxylic acids (i.e. having at least two carboxy groups) may be used in the copolmyer of the present invention. Similarly, anhydrides, chlorides and esters of these acids are suitable. Preferred are the dicarboxylic acids and anhydrides, chlorides and esters thereof having the reactive groups in either the para or meta positions.

The acid, anhydride or ester is preferably utilized in the amount of about 5 percent to about 50 percent by weight of the final copolymer. Illustrative aromatic acids include phthalic acid, isophthalic acid, terephthalic acid, diphenic acid, hemimellitic acid, trimellitic acid, dichlorophthalic acid, etc.

Particularly preferred polycarboxylic acids are the aromatic dicarboxylic acids, containing from 6 to 10 carbon atoms wherein the two carboxyl groups are attached directly to the aromatic nucleus such as the phthalic acids, and preferably isophthalic acid, terephthalic acid mixtures of isophthalic acid and terephthalic acid and anhydrides, chlorides, and esters thereof.

In some cases it may be desirable to utilize other forms of the acids such as the acid anhydrides or acid chlorides, such as phthalic anhydride or trimellitic anhydride.

The esters of the polybasic acids may be produced by an ester-exchange reaction. Preferred derivatives to be used for this purpose comprise the esters of the abovedescribed acids and the lower saturated monohydric alcohols, preferably those alcohols containing from 1 to 5 carbon atoms, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol and amyl alcohol.

Examples of other suitable materials include trimellitic anhydride; pyromellitic benzophenone dianhydride; a benzophenone dicarboxylic acid such as benzophenone -4,4'dicarboxylic acid, 3,3, 4,4 benzophenone tetracarboxylic dianhydride; dimethylterephthalate; dimethylisophthalate, terephthaloyl chloride; isophthaloyl chloride, and l, l, 3, trimethyl -5-carboxy-3-(p-carboxyphenyl) indan. In addition, polycarboxylic aliphatic acids such as adipic acid, maleic acid, glutaric acid, succinic acid, etc. may be used.

Preferably, when the resin composition is used as an enamel for wire, metal drier in an amount of 0.2 to 1.0 percent metal based on total solids is used. Typical metal driers include the zinc, lead, calcium or cadmium lineoleates, octoates and resinates of each of the metals. For example, zinc resinate, cadmium resinate, lead linoleate, calcium linoleate, zinc naphthenate, lead naphthenate, calcium naphthenate, cadmium naphthenate, zinc octoate and cadmium octoate may be used. Polyvalent metal driers such as manganese and cobalt naphthenate can also be employed. A tetraalkyl titanate can be used in small amounts, i.e. 0.001 to 4.0 percent by weight titanium metal of the total solids, in place of the metal drier. Typical titanates are tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetraoctyl titanate, tetramethyl titanate, etc.

When used as a wire enamel, the resin is to be diluted with a suitable solvent such as cresylic acid. The individual cresols present in the acid can also be used but it is preferred to use a commercial available cresylic acid mixture. It is also frequently desirable to dilute the cresylic acid with an aromatic hydrocarbon such as coal tar, petroleum naphtha, xylene etc.

The present invention is further described by the following examples wherein there is illustrated wire coatings with good heat aging properties which are less expensive than the traditional THEIC based resins. The resins contain an organo silicon compound only for the purposes of dry lubricity.

EXAMPLE 1 To a reaction vessel equipped with a condenser, stirring rod, and gas inlet tube, the following materials were added in the proportions indicated:

Parts by Weight In this example and the subsequent examples the l,3-dihydroxydiethyl 5,5'dimethyl hydantoin actually includes a solution of 84-85% by weight and 15-16 percent by weight Substantially pure 1,3-dihydroxydiethyl 5,5'dimethyl hydantoin yields essentially the same results as this solution. The temperature was raised rapidly to C, whereupon 3.3 parts of litharge were added with 100 parts of xylene. The temperature was held at C for 2-6 hours. Nitrogen was used as a purge to remove xylene and other small fractions. The temperature was then allowed to rise to 220240C and when the viscosity reached a clear hard pill stage the mass was quenched with cresylic acid.

The above polymer was diluted using a solvent ratio 60 parts cresylic acid and 40 parts of aromatic hydrocarbon solvent. The enamel was placed on 18 gauge copper magnet wire. The coated wire had good Class 180C NEMA properties.

EXAMPLE 2 Following the procedure set forth in Example 1, the following formula was prepared:

Parts by Weight Dimethylterephthalate 350.0 Tris( Z-hydroxyethyl )isocyanurate (THElC) 250.0 l,3-dihydroxydiethyl 5,5dimethyl hydantoin 108.0 Trimethylolpropane 16.0 Diphenylsilanediol 3.9 Litharge (as alcoholysis catalyst) 09 Xylene (as azeotrope) 100.0

The resulting polymer was applied to wire as a base 5 coat and topcoated with an amide-imide resin. The resultant wire passed all tests for NEMA Class 180C.

EXAMPLE 3 Following the general procedure set forth in Example l, the following formulation was prepared:

Parts b Wei ht Ethylene glycol 1,3-dihydroxyethyl-5,5'dimethyl hydantoin 16.52 Terephthalic acid 32.57 lsophthalic acid 6.88 Tris( Z-hydroxyethyl )isocyanurate (THElC) 26.61 Diphenysilanediol 0.60 Tetraoctyl titanate 0.20 Cresylic acid 8.26

EXAMPLE 4 Following the general procedure set forth in Example 1, the following formula was prepared:

Parts b Wei ht lsophthalic acid 1 l3 Terephthalic acid 529 Tris( Z-hydroxyethyl )isocyanurate 5O (THEIC) 216 Glycerin 76 Ethylene glycol 237 Diphenyl silanediol l0 Tetraoctyl titanate 3 The reaction temperature was allowed to rise to 2l0-245C. over a period of 6 to 16 hours. The resultant polymer was then diluted using a solvent ratio of lsophthalic acid 12 parts cresylic acid and 30 parts of aromatic hydrocarbon solvent to form a wire enamel. The enamel was cured on AWG 18 copper wire. A tabulation of the properties of this enamel, prepared without a hydantoin component, and with a nylon topcoat, is presented in Table l.

1, the following formula was prepared:

Parts by Weight Terephthalic acid 529 Trishydroxyethylisocyanurate 216 Glycerine 76 Ethylene glycol 159 l,3-dihydroxyethyl-5,5-dimethyl hydantoin 270 Diphenyl silanediol 9.9

Tetraoctyl titanate 1.5

The temperature of the reaction was allowed to rise to 220C. over a period of 9 to 18 hours. The polymer was then diluted using a solvent ratio of 70 parts cresylic acid and 30 parts of aromatic hydrocarbon solvent to form a wire enamel. The enamel was then cured on AWG 18 copper wire. The properties of the enamel with and without a nylon topcoat, are tabulated in Table 1. In comparison to the enamel of Example 4, an improvement in heat shock (450C), dielectric strength(500 volts/mil) and burnout resistance (50 seconds) were observed. Accordingly, a comparison of Examples 3 and 5 with Example 4 clearly shows the beneficial properties produced by a reactive hydantoin in the THEIC based resin. Similar results are obtained with other hydantoin based compounds having, for example, reactive l-l, COOl-l, alkoxy, NH groups and the like.

EXAMPLE 6 Following the general procedure of Example 1 part of the terephthalic acid was replaced with a hydantoin acid as follows:

' Parts b Wei ht Terephthalic acid 109 [,3 Dicarboxy ethyl-5,5dirnethyl hydantoin 178 Trishydroxyethylisocyanurate 146 l,3-dihydroxyethyl 5,5 'dimethyl hydantoin 91 Ethylene glycol 45 Diphenyl silanediol 3.2 TOT 1.0

EXAlglPLE EXAMPLE EXAMPLE EXAMPLE 4 5 6 with without with with without with without topcoat topcoat topcoat topcoat topcoat topcoat topcoat [X l IX [X IX I IX Snap X 1870 1800 2000 1800 1300 2000 I670 Dielectric volts/ 3250 3300 2800 3300 3300 2900 2300 in Heat Shock (C) 200 140 175 fail 210 250 Cut through 275 370 260 275 320 260 300 Emersion scrape 32 24 22 23 12 30 28 (lbs) Burnout resistance 500 454 417 467 425 450 (sec) What is claimed is:

1. A resin composition having hydantoin and isocyanurate radicals in the polymer backbone which comprises the reaction product of:

a. a monomeric hydantoin compound having the 5 structural formula 15 wherein A is H, OH, ROH, COOH, RCOOOH, NH RNHQ or (OR) OH wherein R is (CH and y is 1-5, x is an integer in the range of l to 10, R -R where R and R are C -C alkyl groups; and, B is H, OH, ROH, COOH, RCOOH, NH RNH or a C C alkyl group, or dimers or trimers of said monomeric hydantoin compound;

b. an aromatic carboxylic acid having at least two carboxy groups or an anyhydride, ester, or chloride of said acid;

c. tris (2-hydroxyethyl) isocyanurate, as a polyhydric alcohol component; and

d. said reaction effected at a temperature of about 150C to about 280C.

2. A resin composition according to claim 1 wherein up to 50 equivalent percent of the isocyanurate is replaced by another polyhydric alcohol.

3. A resin composition according to claim 2 wherein said alcohol is ehtylene glycol.

4. A resin composition according to claim 1 wherein said carboxylic acid is terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid.

5. A resin composition according to claim 1 wherein said hydantoin compound is l, 3 -dihydroxyethyl 5, 5'- dimethyl hydantoin.

6. A resin composition according to claim 1 wherein said composition includes a tetraalkyl titanate.

7. An electrical conductor having a coating of the composition of claim 1.

8. A resin composition according to claim 1 wherein said reaction product comprises about 5-50 percent by weight of said hydantoin compound, about 5-50 percent by weight of terephthalic acid, isophthalic acid or an anhydride, ester or chloride of said acid, and about 5-50 percent by weight tris (2-hydroxyethyl) isocyanurate. v

9. A resin composition according to claim 8 wherein said hydantoin compound is l, 3 dihydroxyethyl 5 5' dimethyl hydantoin.

10. An electrical conductor having a coating of the composition of claim 8.

0 50 UNITED STATES PATENT OFFlCE' I CERTIFICATE OF CORRECTION PatentNo 3.835.121 Dated SeDtefnberlO. 1974 Jerome H; Preston lnvcnlor(s) H is certified that error appears in the above-idcnlified patent and that said Le'llers Pater are hereby corrected as shown below? Column 13 lines 7 through 15 delete the struetlifal formqla 1 now present and' substitute therefor the following structural formula: 1

r n r;-

n-e c o' '5 '-N .A vg I Signed *and sealed this 7th day of Jaqfiet'y- 1975-. Q

Attest: U v

r-rccoyrr. easel- 1 ,112. c. MARSHALL [bk N51 Attestin'g Officer Commissioner fojf Patents 

2. A resin composition according to claim 1 wherein up to 50 equivalent percent of the isocyanurate is replaced by another polyhydric alcohol.
 3. A resin composition according to claim 2 wherein said alcohol is ehtylene glycol.
 4. A resin composition according to claim 1 wherein said carboxylic acid is terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid.
 5. A resin composition according to claim 1 wherein said hydantoin compound is 1, 3 -dihydroxyethyl - 5, 5''- dimethyl hydantoin.
 6. A resin composition according to claim 1 wherein said composition includes a tetraalkyl titanate.
 7. An electrical conductor having a coating of the composition of claim
 1. 8. A resin composition according to claim 1 wherein said reaction product comprises about 5-50 percent by weight of said hydantoin compound, about 5-50 percent by weight of terephthalic acid, isophthalic acid or an anhydride, ester or chloride of said acid, and about 5-50 percent by weight tris (2-hydroxyethyl) isocyanurate.
 9. A resin composition according to claim 8 wherein said hydantoin compound is 1, 3 - dihydroxyethyl - 5, 5'' - dimethyl hydantoin.
 10. An electrical conductor having a coating of the composition of claim
 8. 